Environmental barrier coating for enhanced resistance to attack by molten silicate deposits

ABSTRACT

An environmental barrier coating, comprising a substrate containing silicon; an environmental barrier layer applied to said substrate; said environmental barrier layer comprising a rare earth composition.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No. 15/998,731 filed Aug. 16, 2018.

BACKGROUND

The disclosure relates to an article comprising a substrate containing silicon and an environmental barrier coating (EBC) which functions as a protective environmental barrier coating and inhibits the formation of gaseous species of Si, particularly Si(OH)_(x) when the article is exposed to a high temperature, aqueous (steam) environment.

Ceramic materials containing silicon and metal alloys containing silicon have been proposed for structures used in high temperature applications as, for example, gas turbine engines, heat exchangers, internal combustion engines, and the like. A particular useful application for these materials is for use in gas turbine engines which operate at high temperatures in steam-laden environments.

It has been found that these silicon containing structures can recess and lose mass as a result of formation of volatile silicon species, particularly Si(OH)_(x) and SiO when exposed to high temperature, steam-laden environments.

It is believed that the process involves oxidation of the silicon containing structure to form silica on the surface followed by reaction of the silica with steam to form volatile species of silicon such as Si(OH)_(x). Naturally it would be highly desirable to provide an external barrier coating for silicon containing substrates which would inhibit the formation of volatile silicon species, Si(OH)_(x) and SiO, and thereby reduce recession and mass loss.

SUMMARY

In accordance with the present disclosure, there is provided an environmental barrier coating, comprising a substrate containing silicon; an environmental barrier layer applied to the substrate; the environmental barrier layer comprising a rare earth composition.

In another and alternative embodiment, the substrate comprises a ceramic matrix composite material.

In another and alternative embodiment, the environmental barrier layer comprises a rare earth apatite.

In another and alternative embodiment, the environmental barrier layer comprises RE₈Ca₂ (SiO₄)₆O₂.

In another and alternative embodiment, the environmental barrier layer comprises an apatite comprising Ca₅F(PO₄)₃.

In another and alternative embodiment, the Ca can be substituted with Mg, Fe, Na, Sr, and Mn.

In another and alternative embodiment, the substrate comprises at least one of a turbine vane and a turbine blade.

In another and alternative embodiment, the environmental barrier coating further comprises a protective layer applied on the environmental barrier coating.

In another and alternative embodiment, the environmental barrier layer comprises an apatite comprising M^(I) ₄M^(II) ₆(SiO₄)₆X₂ in which M^(I) are seven-fold coordinated cation sites and M^(II) are nine-fold coordinated cation sites, and X is an anion sites that is distinct from the oxygen within the silica tetrahedral.

In another and alternative embodiment, the RE ions sit on both the M^(I) and M^(II) sites and Ca sits on the M^(I) site fitting the formula RE₈Ca₂ (SiO₄)₆O₂.

In another and alternative embodiment, the apatite further comprises Mg and Fe additions.

In another and alternative embodiment, the apatite comprises Ca_(2-x-y)Mg_(x)Fe_(y) where 0>x>1 and 0>y>1.

In another and alternative embodiment, at least one of Ca, Mg, Fe, Sr, Na, K, Ti, and Zr is combined with the rare earth composition.

Other details of the coating are set forth in the following detailed description and the accompanying drawings wherein like reference numerals depict like elements.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross section of an exemplary coating on a substrate containing silicon according to the disclosure.

FIG. 2 is a cross section of an exemplary coating on a substrate containing silicon according to the disclosure.

DETAILED DESCRIPTION

Referring now to FIG. 1 , there is illustrated an environmental barrier coating 10 formed over a substrate 12 of an article 14, configured to inhibit the formation of gaseous species of silicon when the article 14 is exposed to a high temperature, aqueous environment. The substrate 12 can be associated with articles 14 such as, at least one of a turbine vane and a turbine blade, and particularly a gas turbine engine component, such as components in the hot section of the gas turbine engine, including static and rotating components and portions of combustors, and the like.

The substrate 12 can be constructed from materials containing silicon and can be a ceramic matrix composite material, a monolithic ceramic, a silicon-based or silicon containing ceramic substrate or a silicon containing metal alloy. In an exemplary embodiment, the substrate 12 can be silicon containing ceramic material such as, for example, silicon carbide, silicon nitride, silicon oxy-nitride and silicon aluminum oxy-nitride, alkaline earth or rare earth silicate glasses or glass ceramics and combinations thereof. Examples can include barium strontium alumino silicate, strontium alumino silicate, lithium alumino silicate, aluminosilicate, mullite, yttrium silicate, ytterbium silicate, and the like. In accordance with a particular embodiment, the silicon containing ceramic substrate comprises a silicon containing matrix with reinforcing materials 16 such as fibers, particles and the like and, more particularly, a silicon based matrix which is fiber-reinforced.

Particularly suitable ceramic substrates are a silicon carbide fiber-reinforced silicon carbide matrix, a carbon fiber-reinforced silicon carbide matrix and a silicon carbide fiber-reinforced silicon nitride matrix. Particularly useful silicon-metal alloys for use as substrates for the article 14 can include molybdenum-silicon alloys, niobium-silicon alloys, iron-silicon alloys, zirconium, hafnium, titanium, chromium, tungsten, boron, platinum, tantalum, Ti—Si alloys and Mo—Si, Nb—Si and Fe—Si alloys.

Referring also to FIG. 2 , an environmental barrier layer 18 can be applied to the substrate 12 on a surface 20. A protective layer 22 can be applied on the environmental barrier layer 18. The protective layer 22 is configured to resist recession of the Si-containing volatile species when exposed to water vapor or steam. In an exemplary embodiment, the protective layer 22 can include binary or multicomponent oxides such as HfO₂, ZrO₂, or Gd₂Hf₂O₇, Gd₂Zr₂O₇, refractory metal oxides. In other exemplary embodiments, the protective layer 22 can include silicates with low(er) SiO₂ activities. In another exemplary embodiment the protective layer 22 can include (rare earth) RE-monosilicates, disilicates and (alkaline earth) AE alumino silicates, silicates of Hafnium and zirconium.

The environmental barrier layer 18 can include a rare earth (RE) composition, such as rare earth apatites. In an exemplary embodiment the apatite can comprise M^(I) ₄M^(II) ₆(SiO₄)₆X₂ in which M^(I) are seven-fold coordinated cation sites and M^(II) are nine-fold coordinated cation sites, and X is an anion sites that is distinct from the oxygen within the silica tetrahedral. In another exemplary embodiment RE ions sit on both the M^(I) and M^(II) sites while Ca sits on the M^(I) site fitting the formula RE₈Ca₂(SiO₄)₆O₂. Alternatively, the composition may be modified by Mg and Fe additions, to include Ca_(2-x-y)Mg_(x)Fe_(y) where 0>x>1 and 0>y>1. Such that in the RE₈(Ca_(2-x-y)Mg_(x)Fe_(y)) (SiO₄)₆O₂, the Ca, Mg, Fe composition is chosen to maximize chemical stability with the deposits in which the primary chemical specials are Ca—Mg—Fe—Al—Si—O. Alternatively, elements such as Ca, Mg, Fe, Sr, Na, K, Ti, and Zr may be added with the rare earth elements. Particularly, the environmental barrier layer 18 can include RE₈Ca₂ (SiO₄)₆O₂. In another exemplary embodiment the environmental barrier layer 18 can include an apatite comprising Ca₅F(PO₄)₃. The Ca can be substituted with Mg, Fe, Na, Sr, and Mn. These substitutions can occur in the RE₈Ca₂(SiO₄)₆O₂ apatite.

The environmental barrier layer 18 can be present on the substrate 12 at a thickness of greater than or equal to about 0.5 mils (0.0005 inch), preferably between about 3 to about 30 mils and ideally between about 3 to about 5 mils.

The environmental barrier layer 18 can be applied by preparing a surface 20 of the substrate 14. The environmental barrier layer 18 can be applied to the substrate 12 by use of suspension plasma spray, electron-beam physical vapor deposition, or an air plasma spray, as well as, slurry based method including dipping, painting and spraying.

In an alternative embodiment, the environmental barrier coating 10 can be formed as multiple combinations of layers 18. In another alternative embodiment, the environmental barrier layer 18 can be multiple layers 24 of RE based on varying RE concentration. In another alternative embodiment, the environmental barrier coating 10 can be multiple layers of RE based on varying the deposition technique, resulting a varying material properties by layer(s). In an exemplary embodiment the environmental barrier layer 18 can include multiple layers 24 applied by applying a suspension plasma spray layer and then an air plasma spray layer.

In an exemplary embodiment, a bond layer can be added in between the environmental barrier layer 18 and the substrate 12 on top of surface 20 for adhesion and oxidation protection.

An advantage of utilizing the disclosed environmental barrier coating 10 composition that is near equilibrium with the silicate melt can include limited mixing of the silicate melt and the environmental barrier coating 10, thus reducing swelling and phase change in the coating. Another advantage of utilizing the disclosed environmental barrier coating 10 composition that is near equilibrium with the silicate melt can include a limited chemical reaction between the environmental barrier coating 10 and the silicate melt that can result in limited new phase formation. This limitation can decrease the strain induced in the top layer of the coating 10 as a result of a mismatch of coefficient of thermal expansion between the reaction products, thus increasing the life of the coating 10.

There has been provided a coating. While the coating has been described in the context of specific embodiments thereof, other unforeseen alternatives, modifications, and variations may become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations which fall within the broad scope of the appended claims. 

1-8. (canceled)
 9. An environmental barrier coating, comprising: a substrate containing silicon; an environmental barrier layer applied to said substrate; said environmental barrier layer comprising a rare earth composition; wherein said environmental barrier layer comprises an apatite comprising M^(I) ₄M^(II) ₆(SiO₄)₆X₂ in which M^(I) are seven-fold coordinated cation sites and M^(II) are nine-fold coordinated cation sites, and X is an anion sites that is distinct from the oxygen within the silica tetrahedral.
 10. The environmental barrier coating of claim 9, wherein RE ions sit on both the M^(I) and M^(II) sites and Ca sits on the M^(I) site fitting the formula RE₈Ca₂ (SiO₄)₆O₂.
 11. The environmental barrier coating of claim 9 wherein said apatite further comprises Mg and Fe additions.
 12. The environmental barrier coating of claim 11 wherein said apatite comprises Ca_(2-x-y)Mg_(x)Fe_(y) where 0>x>1 and 0>y>1.
 13. The environmental barrier coating of claim 9 wherein at least one of Ca, Mg, Fe, Sr, Na, K, Ti, and Zr is combined with the rare earth composition. 